JPS6145247A - Color graphic recording material having yellow-dir coupler - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a color photographic recording material having at least one light-sensitive silver halide emulsion layer containing a yellow coupler which releases a development inhibitor during the color development process.

In color development, diffusible substances are distributed in an imagewise manner during the development process.
It is known that these substances can inhibit the development of silver halide. Such compounds are called D
It is known as an IR compound [DIR = development inhibitor releasing property].
releasing)], the DIR compound has an inhibitory group (i
inhibitor group) and react with the oxidation products of the color developer to form a dye (DIR coupler), or release the inhibitor not simultaneously with the formation of the dye. It is possible. Compounds of the last mentioned type are also called DIR compounds in the strict sense.

DIR compounds are described, for example, in U.S. Pat. No. 3,
No. 148,062, No. 3, 227.

No. 554, No. 3,615,506 and No. 3.6
No. 17,291.

The released development inhibitor is most often a heterocyclic mercapto compound or a benzotriazole derivative. D which couples to form a predominantly colorless product
Information about IR compounds can be found, for example, in US patents (U.S.
S-A) No. 3,632.345, German Patent Application (DE-A) No. 2,359,295 and DE-A No. 2
A number of photographic effects that affect the amount of zero images can be obtained through the use of DIR compounds. These effects include, for example, a reduction in gradation, finer color grains, improved sharpness through the so-called edge effect, and improved color purity and uniformity through the so-called layer effect.
See the following publication: Development Inhibitor Releasing (DIII Couplers in Color Photography)
Inhibitor Releasing (DIR)
Couplers) J *C.R. Bar (C,R
, Barr), J.R. Sartle (J.R.,
Third Le) and P.W. Pittum (P.
graphic 5science and E
ngineering) 13.74 (1969).

DIR compounds have the advantage over DIR couplers that couple to produce colored compounds, allowing the use of one and the same compound in all light-sensitive layers of a color photographic recording material, regardless of the color to be produced. It can be used generally. DIR couplers, on the other hand, are usually only used in some photosensitive layers if the side density of the color produced by DIR couplers in other layers is not acceptable because of the color they produce. However, this advantage of DIR compounds has the disadvantage that DIR compounds are generally less reactive than DIR couplers. Therefore, photographic implementation has been limited to the use of DIR couplers in most cases and as needed.

Two or more different DIR couplers have been used in the same recording material, and layers with different spectral sensitivities have been associated with different DIR couplers according to the color to be produced from the coupler.

German Patent Application No. 2,842.
No. 063 discloses DIR couplers derived from yellow couplers and containing a 3-furkylthio-1,2,4-triazolyl group as a releasable inhibiting group.

When the DIR couplers described in the aforementioned literature are used in a blue-sensitive silver halide emulsion layer, they improve the color gradation (col.) in this layer.

ur gradation) is considerably reduced, but the effect on adjacent silver halide layers, especially adjacent green-sensitive and/or red-sensitive silver halide emulsion layers, is relatively small. Therefore, known DIR couplers exhibit slight interimage effects.
effect).

It is an object of the present invention to provide color photographic recording materials containing yellow DIR couplers that are capable of producing relatively strong interimage effects.

The present invention has at least one light-sensitive silver halide emulsion layer and, in association therewith, a DIR coupler, said DIR coupler having a releasable 1,2,4-triazole group attached to a yellow coupler. A color photographic recording material supporting in a coupling position said DI
R coupler is represented by the following formula (I), where R1 represents a linear or branched alkyl, an optionally substituted aryl, or -NR5R6, and 1(2, R5 is H or 1-3 represents alkyl having 5 carbon atoms.

R3 and R6 represent alkyl having 1 to 18 carbon atoms or optionally substituted aryl, R4 represents alkyl having 5 to 12 carbon atoms, and Fu is optionally substituted. It relates to a color photographic recording material, characterized in that it exhibits a good frill group and corresponds to the following.

The alkyl group represented by R1 has 1 to 184 PJ carbon atoms. It can be linear or branched and is preferably a tert-alkyl group.
Examples are: methyl, ethyl, propyl, isopropyl, n-butyl.

tert-butyl, E-7mil, and 1,1,3.3-tetramethyl-butyl, the alkyl group can also be a cyclic or bicyclic group, such as a norbornyl group or an adamantyl group. .

The aryl group represented by R1 or R3 is in particular phenyl, which is, for example, alkyl, alkoxy, halogen.

Can be substituted with carbamoyl, sulfamoyl or acylamino. Acyl groups can be derived from aliphatic or aromatic carboxylic acids or from sulfonic acid monoesters or carbamic acids.

The alkyl group represented by R4 can be straight-chain or branched and can be substituted by aryl (eg benzyl).

The symbol Fu is attached via the 2- or 3-position and can contain further substituents, for example furyl-2,2-methylfuryl-3, or 5-nitrofuryl-2.

According to formula (I), the 1,2,4-triazole ring is attached to the coupling position of the yellow coupler by one of the two adjacent nitrogen atoms.

However, it is not completely clear to date whether this compound corresponds to the truth, so the formula (I)
, 2.4-triazole ring is intended to represent the corresponding isomer in which the ring can be attached to the coupling position through the nitrogen atom of the other ring.

Examples of suitable yellow DIR couplers according to the invention are shown in Table 1 (R2=H; Fu=frill).

g, qc,, ooc COOC1,H □ The DIR coupler of the present invention corresponding to formula (I) has the formula (I
I) In the formula.

R]~R3 has the meaning already indicated, and Hal is a halogen atom, especially a! A known α-halogenoacetanilide corresponding to the formula (m
) in which R4 and Fu have the meanings indicated. The reaction is preferably carried out in an organic solvent, such as dimethylformamide, acetonitrile or acetone, in the presence of a base, such as triethylamine or caustic potassium.

The corresponding triazole of formula (III) is the corresponding 3-
It can be obtained by reacting mercapto-1,2,4-triazole with a suitable alkyl halide or aralkyl halide.

The triazoles of formula (m) occur in different tautomeric forms and therefore have different resonance boundary structures (mesomeric bo
undary 5structureS) can be attributed to the corresponding ion, and it is thought that the bond with the carbon at the coupling position in the condensation reaction can occur through any of the ring nitrogen atoms present, which is due to the occurrence of the corresponding isomer. Explain. However, this mechanism does not affect the useful properties of the DIR coupler according to the invention;
A detailed explanation of the structures of the possible isomers is therefore unnecessary.

The method of manufacturing a DIR coupler according to the invention is detailed below with reference to the example of DIR coupler 4.

Compound 4 a) 3-hexylthio-5-(furyl-2)-1,
500 g of 2,4-triazole 3-mercapto-5-(furyl-2)-1,
2,4-triazole, 530 g hexyl bromide and 168 g caustic potassium in 3000 ml methanol
The KBr precipitated in the course of the reaction heated under reflux for 0 hours was filtered off with suction, and about 2500 ml of methanol was filtered off; and the residue was taken up with water. The precipitated product was filtered off with suction and dried.

Yield: 722g Melting point = 96°C (after recrystallization from cyclohexane).

b) Compound 4 356 g of α-(4-methoxybenzoyl)-α-chloro-2-hexysubyloxy-5-N-methylsulfamoylacetanilide and 140 g of the triazole prepared according to a) with 63 g of caustic potassium 150
The reaction solution, stirred for 15 hours at room temperature in 0 ml of 7cetanilide, was poured into 1500 ml of 10% 141 acid and the oil thus obtained was dissolved in 500 ml of
1 in toluene. The solution in toluene was concentrated by evaporation, the oily residue was poured into 1300 ml of cyclohexane, the product crystallized from cyclohexane was filtered with suction and air-dried.

Yield: 300g Melting point: 63-65°C.

The compounds according to the invention are suitable for use as yellow DIR couplers in color photography, especially in multilayer recording materials. As yellow couplers they are preferably used in or in conjunction with light-sensitive silver halide emulsion layers having a predominant sensitivity in the blue spectral region of visible light.

The particular advantages of the yellow DIR couplers according to the invention, namely their relatively slight inhibitory effect on the development in the layers with which they are associated, as well as their relatively strong inhibitory effect on the development in adjacent layers to which they are not associated, are, of course, numerous. J
! ! ! This is particularly important in Type I color photographic recording materials, which multilayer color photographic recording materials contain, in addition to a primarily blue-sensitive silver halide emulsion layer, other materials that are primarily sensitive to the green or red spectral region of visible light. Contains a photosensitive silver halide emulsion layer. Technically advanced color photographic recording materials contain at least one light-sensitive silver halide emulsion layer unit having associated color couplers for each of the three spectral regions, blue, green and red. Each of these silver halide emulsion layer units may consist of l or more silver halide emulsion sublayers, and if several such layers are formed, they are generally spectrally identical. Although it is sensitized to the area,
They may differ in their overall sensitivity, the type of silver halide used, the type of color coupler used, the coupler to silver ratio and perhaps also other physical or chemical parameters. Individual partial layers with identical spectral sensitivities can be spatially combined to form a silver halide layer unit, or (parts) H that are sensitive to one part of the visible spectrum can have different spectral sensitivities. It can be arranged to be located between two partial layers of the sensitive layer unit. A light-insensitive intermediate layer or branching layer is advantageously provided between two layers with different spectral sensitivities.

As previously mentioned, at least one color coupler is associated with each individual silver halide emulsion layer unit.

The term "associated" means that the silver halide emulsion layer unit and the color coupler are such that when development occurs, interaction between them occurs to produce an imagewise correspondence between the resulting silver image and the resulting color image. , meaning arranged in relation to each other. For this purpose, the color couplers can be incorporated into one or more of the silver halide emulsion partial layers of the silver halide emulsion layer unit or into a layer of non-light-sensitive binder adjacent thereto.

Color couplers, which may be associated with two or more sublayers of a silver halide emulsion layer unit, are used in the process of color development to produce the same color 1, usually complementary to the color of light to which the light-sensitive silver halide emulsion layer is primarily sensitive. The red-sensitive silver halide emulsion layers therefore have at least one color coupler associated therewith to produce a cyan partial color image, which does not necessarily have to be identical only insofar as they produce a cyan partial color image. It has a phenol or α-naphthol series coupler. In conjunction with the green-sensitive silver halide emulsion layer there is at least one color coupler which produces a magenta partial color image, and these color couplers are usually of the 5-pyrazolone or indasilone series. In conjunction with the blue-sensitive silver halide emulsion layer there is at least one color coupler that produces a yellow partial color image, these color couplers generally having open-chain ketomethylene groups. Color couplers of these types are known in large numbers and have been described in numerous patent specifications. See, for example, the following references: "Farbkupler", W. Pelz. Author: Mitteilungen Aus and Den-
7 Horschungslapolatrien-der Agfa.

Leverkusen/Munich
gen aus forschungslabor
Atorien der Agfa, Level
kusen/M5 nchen)”, V.

1, I [I, page 111 (1961) and VENKATARAMAN 7.

“The chemistry of synthetic dyes”
of 5ynthetic Dyes)” +V
o1.4, 341-387. Academic Press (A
Academic Press) (1971).

The color coupler can be a conventional 4-equivalent coupler or a 2-equivalent coupler, the latter requiring less silver halide for color production. As is known, 2-equivalent couplers differ from 4-equivalent couplers in that they have a substituent in the coupling position that is cleaved off during the coupling process. The latter couplers include both those that are virtually colorless and those that have a brighter color that is replaced by the color of any image dye that is lost during the color-bling process. additionally present in and 11. masking coupler to compensate for unwanted side densities.

u l e r) role can be played there. Two-equivalent couplers also include known white couplers that do not form dyes on reaction with oxidation products of color developers, as well as those that are released as diffusible development inhibitors on reaction with oxidation products of color developers. Included are known DIR couplers, which are couplers that contain a cleavable group in the coupling position for the purpose of binding. This category of 2-equivalent couplers also includes one yellow DIR coupler of the present invention.

Mixtures of color couplers can be used when seeking to obtain the desired reactivity of a particular color configuration. For example, a water-soluble coupler can be used in combination with a hydrophobic water-insoluble coupler.

Although both the color couplers and the yellow DIR couplers according to the invention are generally incorporated in their layers in non-diffusive form, in some cases it is possible to use color couplers with some limited tendency to diffuse. It's advantageous. Image dyes formed from color couplers during development will generally no longer be diffusive in one layer.

In the present invention, color images are developed using color couplers (
chromogenic c) Although described with reference to a recording material produced by development, the invention is in no way limited to such materials; the gradation of the layer containing the yellow DIR coupler according to the invention as well as the effect on adjacent layers; is completely independent of the nature of the other color-forming compounds used. Other types of color-forming compounds, such as developer dyes or dye-releasing compounds of the type used in dye diffusion photography, can therefore be used as the aforementioned color couplers. However, one constant prerequisite is that the development is controlled by a diffusible development inhibitor, in this case 3-alkylthio-5-furyl-1,2,
Development should be carried out under conditions such that 4-trizole is released into the imaging process to the extent that it was previously exposed. This means that: 1 the color photographic recording material according to the invention is developed in the presence of a developer compound, where the oxidation products of said developer compound react with the yellow DIR coupler according to the invention to release a development inhibitor; means. Examples of suitable developer compounds of this type include, for example, the conventionally used p-phenylenediamine containing free primary amino groups.

The amount of yellow DIR coupler according to the invention used in the layer can be varied within wide limits according to the requirements, e.g.
It can vary within the range of 10-4 to 50 X l O-'1 mol/m'. A particularly suitable result is 1, for example 1
Yellow DIR coupler according to the present invention from 1.0 to 5.0
It is obtained by using an amount within the range of 1 mol/m2 of XlO-4.

The present invention will be illustrated based on the arrangement of layers described below. To create this arrangement, the layers shown are applied to the cellulose triacetate transparent one-layer support in the order in which the layers are shown, anti-halizing layer and adhesive layer. The quantities stated are based on 1 m2 in each case.

The amount of silver applied is based on the corresponding amount of AgNO3.

1. 3.5g (7) 600mg of AgNO3 + 30mg of cyan coupler corresponding to formula 7).

A red-sensitized silver iodobromide emulsion (5 mole % Age) of a DIR coupler corresponding to the formula, and 60 mg of a magenta coupler corresponding to the formula, and 2.5 g of gelatin. a red-sensitized silver iodobromide emulsion (8 mole % AgI) of 3.0 g AgN (h) and 200 mg 731 cyan coupler and 2.7 g gelatin; 3. Interlayer containing 0.8 g of gelatin and 0.1 g of 2°5-diisooctylhydroquinone: 4, 2.5 g of AgN0z and 800 mg of magenta coupler corresponding to formula (7), 25 mg of formula % a less sensitive green-sensitive layer containing the corresponding DIR coupler, 90 mg of masking coupler corresponding to the formula, and 2.6 g of gelatin green-sensitized silver iodobromide emulsion (6 mol% AgI); 5, 2; Ogc7) AgNO3 and 250mg layer 4
a green-sensitized silver iodobromide emulsion (10 mole % AgI) of magenta blur and 1.7 g of gelatin; 6. colloidal silver producing a yellow density of 0.7; and one layer of yellow filter containing 0.6 g of gelatin; 7. 1. A less sensitive blue-sensitive layer containing a yellow coupler corresponding to the formula Og of AgNO3 and 700 mg of the DIR compounds shown in Table 2 below, and a silver iodobromide emulsion of gelatin (5 mol% AgI) of 0.9 g. 8, 1.3gc7) Higher sensitivity blue sensitive layer containing a blue sensitized silver iodobromide emulsion (10 mol % AgI) of AgNOz and 300 mg layer 7 yellow coupler and 0.7 g gelatin; 9 , one layer of birch containing 0.6 g of gelatin.

The couplers in layers 1, 2.4, 6.7 and 8 and the diisooctylhydroquinone in layer 3 are the DIR couplers used in layer 7 used in the form TM of emulsion (1:1) with tricresyl phosphate. and the resulting suppression values for three partial images, yellow, magenta and cyan, are shown in Table 2 below.
Regression in color density measured behind green or red filters (ΔDb, ΔDg
, ΔDr) compared with that of a recording material containing no DIR coupler in layer 7, based on an absolute density ΔDn=1.5 over the minimum density Dmin, showing the 1114 constant behind the green and red filters. The corresponding quotient of inhibition for the inhibition value given is also written: Qg=ΔDg/ΔDb.

Q r = Δ0 r /ΔD b After exposure to light through a gray wedge, development was carried out in “The British Journal of Photography 4-(T
he Br1tish Journal of
Photography)”.

1974.1974, pages 597 and 598.

As Table 2 shows, the yellow DIR coupler according to the invention used in the less sensitive blue-sensitive layer significantly suppressed development in the green-sensitive layer and therefore significantly reduced the gradation of the magenta partial color image, which In contrast, the suppression in the blue-sensitive layer is relatively slight. This is Q
The Qg value is clearly greater than 1, on the other hand, the yellow DIR coupler A used for comparison.
, B, C, D and E have an effect on the gradation of the mainly yellow partial color image.

The yellow DIR coupler according to the invention is also clearly superior in its effect on more distantly located red-sensitive layers.

The color separation and graininess and sharpness of the recording material are
There is therefore a considerable improvement when using the compounds according to the invention.

The following is the yellow DIR coupler used for comparison:

Claims (1)

Claims: 1. at least one light-sensitive silver halide emulsion layer and, associated with this layer, a DIR coupler;
R coupler is a color photographic recording material which supports in the coupling position a yellow coupler attached to a cleavable 1,2,4-triazole group,
The R coupler has the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, R^1 represents linear or branched alkyl, optionally substituted aryl, or -NR^5R^6 , R^2, R^5 represent H or alkyl having 1 to 3 carbon atoms, and R^3, R^6 represent alkyl having 1 to 18 carbon atoms or optionally substituted aryl. A color photographic recording material corresponding to the following, R^4 represents an alkyl group having 5 to 12 carbon atoms, and Fu represents an optionally substituted furyl group. 2. said DIR coupler is contained in a predominantly blue-sensitive silver halide emulsion layer, and the recording material contains at least one other silver halide emulsion layer that is predominantly green-sensitive or predominantly red-sensitive; A recording material according to claim 1 containing the recording material. 3. at least one predominantly blue-sensitive silver halide emulsion layer unit associated with at least one yellow coupler, at least one predominantly green-sensitive silver halide emulsion layer unit associated with at least one magenta coupler, and at least one A color photographic recording material having a predominantly red-sensitive silver halide emulsion layer unit associated with a cyan coupler, wherein at least one partial layer of the predominantly blue-sensitive silver halide emulsion layer unit has the following formula: etc.▼ In the formula, R^1 represents linear or branched alkyl, optionally substituted aryl, or -NR^5R^6, and R^2 and R^5 are H or Represents alkyl having 1 to 3 carbon atoms, R^3 and R^6 represent alkyl having 1 to 18 carbon atoms or optionally substituted aryl, and R^4 represents 5 to 12 carbon atoms. 1. A color photographic recording material, characterized in that it contains a compound corresponding to the following, wherein Fu represents an optionally substituted furyl group.